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Abstract:

A method of removing oil from a mixture of tool steel swarf granular
material and oil. The abstract of the disclosure is submitted herewith as
required by 37 C.F.R. §1.72(b). As stated in 37 C.F.R.
§1.72(b): A brief abstract of the technical disclosure in the
specification must commence on a separate sheet, preferably following the
claims, under the heading "Abstract of the Disclosure." The purpose of
the abstract is to enable the Patent and Trademark Office and the public
generally to determine quickly from a cursory inspection the nature and
gist of the technical disclosure. The abstract shall not be used for
interpreting the scope of the claims. Therefore, any statements made
relating to the abstract are not intended to limit the claims in any
manner and should not be interpreted as limiting the claims in any
manner.

Claims:

1-15. (canceled)

16. An industrial method of removing cutting oil from tool steel swarf in
an extraction vessel, said method comprising the steps of: (a) opening
said extraction vessel and loading said tool steel swarf into said
extraction vessel; (b) closing said extraction vessel to seal said tool
steel swarf therein; (c) removing at least about 89% by weight of said
cutting oil from said tool steel swarf by flowing supercritical carbon
dioxide through said tool steel swarf at a pressure of at least about
4300 PSI and at a temperature of at least about 50.degree. C.; (d)
separating said tool steel swarf from said supercritical carbon dioxide
containing cutting oil; and (e) opening said extraction vessel and
removing said tool steel swarf from said extraction vessel.

17. The method according to claim 16, wherein said step (c) comprises
removing at least about 89% by weight of said cutting oil from said tool
steel swarf essentially solely by flowing supercritical carbon dioxide
through said tool steel swarf.

19. The method according to claim 16, wherein said cutting oil comprises
a substantially paraffinic mixture of hydrocarbons.

20. The method according to claim 16, wherein said cutting oil comprises
a mixture of hydrocarbons, which mixture comprises about 94.9% by weight
of C29 and higher hydrocarbons.

Description:

BACKGROUND

[0001] 1. Technical Field

[0002] This application relates to a method of removing oil from a mixture
of tool steel swarf granular material and oil.

[0003] 2. Background Information

[0004] This application relates to the process conditions in utilizing
supercritical carbon dioxide (SCCO2) for substantial removal of
residual cutting fluids, either oils and/or water, and at least partial
removal of other contaminants from industrial grindings of tool steels
that may be contaminated with aqueous and/or oil-based residual
contaminates. The contaminant liquid can be recycled for reuse, and the
solids can be recycled or remelted in the smelting process for reuse. If
the contaminants are not removed, they present an environmental hazard
when they are land filled or incinerated.

[0005] Supercritical carbon dioxide is carbon dioxide that is at a
temperature and a pressure greater than Tr=1 and Pr=1. (Tr is T/Tc where
T is the present temperature of the supercritical carbon dioxide and Tc
is the critical temperature. Pr is P/Pc where P is the present pressure
of the supercritical carbon dioxide and Pc is the critical pressure.) Tc,
the critical temperature for carbon dioxide (CO2), is 31.1 degrees
Celsius (° C.), or 304.1 degrees Kelvin (K), and Pc is 73
atmospheres (atm) or about 1073 pounds per square inch (PSI).

[0006] In more general terms, supercritical carbon dioxide refers to
carbon dioxide that is in a fluid state while also being at or above both
its critical temperature and pressure. Carbon dioxide usually behaves as
a gas in air at standard temperature and pressure (STP) or as a solid
called dry ice when frozen. If the temperature and pressure are both
increased from standard temperature and pressure to be at or above the
critical point for carbon dioxide, it can adopt properties midway between
a gas and a liquid. More specifically, it behaves as a supercritical
fluid above its critical temperature (31.1° C.) and critical
pressure (73 atm), expanding to fill its container like a gas but with a
density like that of a liquid. The supercritical fluid region of the
phase diagram is defined as a temperature above the critical temperature
(31.1° C.) to a pressure above the critical pressure (73.8 bar or
1070 PSI).

SUMMARY

[0007] At least one possible embodiment of the present application teaches
a method for the removal of oil from a mixture of granular material and
oil using supercritical carbon dioxide. It was found, through
experimentation, that the supercritical carbon dioxide extraction of high
speed steel (HSS) grinding swarf can, in at least one possible embodiment
of the present application, produce a solids high speed steel product
with less than 5% (by weight) cutting oil. In at least one possible
embodiment, there can be as low as 0.44% (by weight) oil in the extracted
solids.

[0008] A typical high speed steel swarf analysis is presented in Table A
as follows:

[0009] The source of the aluminum oxide (alumina) is the grinding media.
The principal source of the silicon dioxide (silica) is diatomaceous
earth. This is often added for ease of filtration in trying to remove as
much oil as possible from the swarf prior to land-filling.

[0010] The following represents the physical and chemical characteristics
of High speed steel grinding swarf:

[0011] Solids:

[0012] High speed steel--same composition as presented in
Table A

[0013] Particle sizes of swarf in Table A--median 400 mesh, or 37
micrometers (μ); particle size diameter (PSD), such as a mean diameter
of the particles, from 10 micrometers to 300 micrometers; particles
generally irregularly shaped and generally not spherical.

[0014] Contaminant:

[0015] A complex mixture of hydrocarbons

[0016]
Mixture, mostly paraffinic, but also some high MW oxy compounds

[0026] In at least one possible embodiment of the present application, the
particle sizes are primarily in the range of 10 to 100 micrometers. If a
screen analysis of dried swarf is completed, at least 50% of the material
by weight will pass through a standard 325 mesh screen. The screen
opening for the 325 mesh screen is 45 micrometers. At least 98% of this
material by weight will pass through a 80 mesh screen which has a screen
opening of about 177 micrometers.

[0027] In a screen analysis of a high speed steel swarf sample, oil was
removed from a mixture of granular material and oil using supercritical
carbon dioxide (CO2). The following Table B presents these results:

In this case, the median size (based on numbers of particles) was 39
micrometers.

[0028] Concerning non-metallic swarf components, diatomaceous earth is
often used in such equipment as Coopermatic Filters to filter swarf from
the grinding oil in manufacturing plants of the tool maker. Another
product which is used in certain tool steel drill making plants that
generate swarf is the Eagle Pitcher CELETOM FW 60.

[0029] This application relates to the process configuration using
supercritical carbon dioxide in order to successfully remove as much as
greater than 98% (by weight) of such contaminants from the feed solids,
since the reuse of such "clean solids" is predicated on a contaminant
level at approximately 0.5% to 2% (by weight). Using carbon dioxide as
the working fluid or extraction solvent, at least one embodiment of the
present application utilizes carbon dioxide cycling in and out of the
supercritical state to convert a metal waste by-product into a reusable
liquid contaminant and substantially liquid contaminant-free solids, both
of which can be reused with relatively small waste. The carbon dioxide
may also be re-circulated and reused.

[0030] It is not necessarily desirable to produce a solids product with 0%
contaminant (oil) since pure metals and/or alloys with high surface areas
per weight, such as high speed steel, can undergo rapid oxidation with
air, especially for very high surface area fines. Not only can the
temperature increases be large, there can or may be auto-ignition, such
as an explosion, of certain metals or alloys. Therefore, from a process
point-of-view, removal of as much contaminant as possible should be
promoted or maximized, while still leaving a minimum amount sufficient to
suppress spontaneous reaction during contact with air (oxygen) during the
handling and transport of the purified solids.

[0031] In this regard, it is sufficient to leave approximately 0.5% to 2%
(by weight) contaminant oil on high speed steel product. For other
examples of metals and alloys, it may be sufficient to leave a different
contaminant level, predicated by the oxidation chemistry for each
specific solid material in the cleansed product.

[0032] For extracted high speed steel swarf solids product, therefore, it
may be sufficient to leave 0.5 to 2% (by weight) residual contaminant for
handling and storage purposes, while re-melting such solids product can
be easily and safely carried out.

[0033] The above-discussed embodiments of the present invention will be
described further hereinbelow. When the word "invention" or "embodiment
of the invention" is used in this specification, the word "invention" or
"embodiment of the invention" includes "inventions" or "embodiments of
the invention", that is the plural of "invention" or "embodiment of the
invention". By stating "invention" or "embodiment of the invention", the
Applicant does not in any way admit that the present application does not
include more than one patentably and non-obviously distinct invention,
and maintains that this application may include more than one patentably
and non-obviously distinct invention. The Applicant hereby asserts that
the disclosure of this application may include more than one invention,
and, in the event that there is more than one invention, that these
inventions may be patentable and non-obvious one with respect to the
other.

BRIEF DESCRIPTION OF THE DRAWINGS

[0034] At least one possible embodiment of the present application will be
described by means of the accompanying drawings, in which:

[0036]FIG. 2 is a diagram showing the process for carrying out the
supercritical carbon dioxide extraction of high speed steel grinding
swarf;

[0037]FIG. 3 is a graph showing further results from supercritical carbon
dioxide extraction of high speed steel grinding swarf;

[0038]FIG. 4 is a graph showing the percentage of oil extracted during a
process of supercritical carbon dioxide extraction of high speed steel
grinding swarf; and

[0039]FIG. 5 is a graph showing the percentage of oil remaining after a
process of supercritical carbon dioxide extraction of high speed steel
grinding swarf has been completed.

DESCRIPTION OF EMBODIMENT OR EMBODIMENTS

[0040] The swarf, as analyzed in Tables A and B, was sent to Supercritical
Solutions LLC, 2845 Rolling Green Place, Macungie, Pa., 28062, to remove
oil from the mixture of granular material and oil, and Table 1 shows the
resulting data. In at least one possible embodiment of the present
application, a small sample of high speed steel swarf was loaded into a
process development unit (PDU), brought to temperature, either by direct
and/or indirect heat transfer, to 24° C., and pressurized to 1700
PSI. The sample was extracted by passing pure subcritical carbon dioxide
through the bed, continuously, over a two-hour (120 min) period. The
sample of initial high speed steel swarf feed contained approximately
12.4%, (by weight) contaminant oil. It should be noted that other samples
of swarf could contain levels of contaminant oil other than 12.4%.

[0041] Samples of treated swarf were taken and analyzed intermittently
over the duration of the experiment. The effluent carbon dioxide from the
bed was depressurized, dropping-out the extracted oil in another,
separate vessel. The samples were analyzed every ten minutes, and after
120 minutes, the bed was depressurized, the contents emptied, and
analyzed. The following Table 1 presents these results:

[0042] In Run 1, the starting feed contained 12.4% oil, and the extracted
sample of high speed steel product contained 10.6% (by weight) oil after
a total processing residence time of 120 minutes. The oil removed from
the feed was approximately 57.1% (by weight).

[0043] Another sample of high speed steel swarf was subjected to the
process development unit and processed at supercritical carbon dioxide
conditions, at 4300 PSI, and at 55 C.°, as noted in Run 2 in Table
1. The oil extracted was approximately 89.6% (by weight) at a residence
time of 120 minutes.

[0044] In Run 3, the pressure was 4350 PSI, the temperature was 50°
C., and the amount of feed in the PDU was approximately one half the
amount in Run 2. From Table 1, it can be noted that the oil removal
increased from 89.6% to 91.6% just by lowering the operating temperature
5° C., from 55 to 50° C. Again, the residence time was 120
minutes.

[0045] In Run 4, the pressure was 5000 PSI and temperature was 60°
C., and the oil removal was approximately 88.9% (by weight) after a
residence time of 100 minutes.

[0046] In Run 5, the temperature was 64/65° C. and a pressure of
5000 PSI was employed. Run 5 produced an oil removal of approximately 95%
(by weight). The residence time was approximately 80 minutes.

[0047] Run 6 was carried out at a pressure of 8700 PSI and a temperature
of 80° C. With a residence time of approximately 50 minutes, a
98.4% (by weight) removal of the contaminant oil was achieved.

[0048] The pressure was 9000 PSI at a temperature of 90° C. in Run
7. A sharp reduction in oil removal was found, down to 95.9% oil removal,
and even with additional variations of pressure up to 9200 PSI and
temperature up to 110° C. (Runs 8, 9, and 10), the oil removal
rates appeared to take a downturn.

[0049] Runs 7 through 11 were carried out at residence times of 55-85
minutes.

[0050] For the Runs presented in Table 1, not only were the conditions of
temperature and pressure closely maintained, bed size and solvent to feed
ratio (gms CO2/gms sample), also known as S/F, were closely
controlled to obtain as high a contaminant removal as possible. In
addition, residence time was carefully studied by taking samples during
the Runs and analyzing the oil contents. These data are best summarized
in FIG. 1.

[0051] Using a continuous process development unit (PDU), carbon dioxide
at the conditions noted was passed through a bed (size noted) of high
speed steel swarf and the contaminant oil removal (as feed) was plotted
against the cumulative amount of carbon dioxide being passed through the
sample over the total residence time, as shown on FIG. 1. Although
end-point data are tabulated in Table 1, at least 5 to 10 data points
collected during the Runs were used to construct Curves A through K, as
shown in FIG. 1. For clarity purposes, some are depicted in FIG. 1 to
elucidate the differences. The region between 8700 PSI and 9200 PSI
represents the contaminant removal, as noted in FIG. 1 for Curves G, H,
and J. Note that the curve letters in FIG. 1 correspond to data points in
the legend.

[0052] From the data in Table 1 and depicted in FIG. 1, it is concluded
that an optimum oil removal is achieved between 8700 PSI and 9000 PSI, or
indeed at 8700 PSI. At 9000 and 9200 PSI, the oil removal decreased from
a maximum of 98.4% to approximately 92% to 96%.

[0053] The process for carrying out the subject supercritical carbon
dioxide substantial extraction of swarf can be generally depicted in
FIGS. 2 and 3. FIG. 2 is a diagram depicting a process using either pure
and/or recycled carbon dioxide. The pumps and heat exchangers are
designed to meet target Tr and Pr conditions at the prescribed solvent
carbon dioxide to feed high speed steel ratios. The size of the "feed and
product beds" are dependent on the physical characteristics of the feed
and the production rate desired. The number of beds can also vary (from 2
as shown in FIG. 2) depending on production rate desired.

[0054] The process depicted in FIG. 2, two parallel stages, can be
designed to yield 98+% oil contaminant removal from high speed steel, and
other similar metallic waste products and other similar oil contaminants
at extraction and desorption pressures of between 5000 PSI and 8700 PSI,
and beyond, and at temperatures between 60° and 110° C. At
5000 PSI and 65° C., a 94.9% oil removal was achieved, and at 8700
PSI and 80° C., a 98.4% oil removal was achieved (see Table 1).
Therefore, it is possible 98+% oil removal could be achieved somewhere
between 5000 PSI and 8700 PSI, and/or beyond. It should be understood
that other process options besides two parallel stages may possibly be
used in at least one possible embodiment.

[0055]FIG. 3, used in conjunction with FIG. 2, is intended to "simulate"
the "cycle" for contaminant removal from high speed steel swarf. The
solubility data (mole fraction oil in carbon dioxide) is estimated from
the reference by J. Yau et al., J. Chem. Eng. Data, 38, 174 (1993)
extrapolated to higher pressures and temperatures. The oil is assumed to
be n-hexatriacontane (C36) and its solubility in supercritical
carbon dioxide used in FIG. 3 to qualitatively depict the "cycle" used in
FIG. 2. Since the contaminant oil in high speed steel swarf is so
complex, as will be described later, herein, most of it is C29+.
Therefore, solubility data in supercritical carbon dioxide for the
highest MW normal paraffin found in the literature was used for FIG. 3.

[0056] Therefore, FIG. 3 is a solubility diagram with Points A through F
depicted from FIG. 2. The only points truly at, or close to, equilibrium
are Points A and B and A', A'', B', and B''. Points C, D, E and F are far
from equilibrium, but at pressures and temperatures depicted on FIG. 3.
Hence, the Points in any one cycle are represented by the Temperatures
and Pressures, and additionally, for Points A, A', and A'', and B, B',
and B'', the solubility of oil in the supercritical carbon dioxide. (All
points A fall on the isobar desired, such as 4300 psi up to 9000 psi.)

[0057]FIG. 4 is a graph in which represents the percentage of oil
extracted during Runs 1-11 using the indicated pounds per square inch PSI
pressure, as shown in Table 1. For instance, in Run 1, 57.1% of the oil
was removed using 1700 PSI. Run 2 resulted in 89.6% of the oil being
removed using 4300 PSI. 91.6% of the oil was removed using 4350 PSI in
Run 3. During Run 4, 88.9% of the oil was removed using 5000 PSI. Run 5
resulted in 94.9% of the oil being removed using 5000 PSI. 98.4% of the
oil was removed using 8700 PSI in Run 6. In Run 7, 95.9% of the oil was
removed using 9000 PSI. Run 8 resulted in 92.9% of the oil being removed
using 9000 PSI. 92.3% of the oil was removed using 9200 PSI in Run 9. Run
10 resulted in 94.9% of the oil being removed in which 9200 PSI was used.
Run 11 resulted in 96.2% of oil being removed using 9200 PSI.

[0058]FIG. 5 is a graph, using information provided in Table 1, to show
the percentage of oil remaining after a process of supercritical carbon
dioxide extraction of high speed steel grinding swarf has been completed.
For instance, in Run 1, 10.6% of the oil remained after using 1700 PSI.
Run 2 resulted in 2.92% of the oil remaining after using 4300 PSI. 91.6%
of the oil remained after using 4350 PSI in Run 3. During Run 4, 3.26% of
the oil remained after using 5000 PSI. Run 5 resulted in 1.52% of the oil
remaining after using 5000 PSI. 0.44% of the oil remained after using
8700 PSI in Run 6. In Run 7, 1.02% of the oil remained after using 9000
PSI. Run 8 resulted in 1.74% of the oil remaining after using 9000 PSI.
1.84% of the oil remained after using 9200 PSI in Run 9. Run 10 resulted
in 1.04% of the oil remaining after 9200 PSI was used. Run 11 resulted in
0.93% of oil remaining after using 9200 PSI.

[0059] Since high speed steel swarf is extremely dense (specific gravity
(s.g.) of approximately 1.6), the sheer weight of the loaded process
vessels at approximately 100 pounds per cubic feet can be substantial. In
addition, loading, processing, and emptying such large vessels in
residence times from 30 to 120 minutes can be a challenge for a
large-tonnage plant. One possible option is to use a fewer number of
large vessels with large weights filled and emptied in a longer period of
cycle time, or another possible option is to use a larger number of
smaller vessels with smaller weights filled and emptied in a shorter
period of cycle time. In at least one possible embodiment, the size and
cycle time for handling such feed and product materials is selected to
promote the supercritical carbon dioxide deep removal of this bulk
contaminant oil.

[0060] It was determined that smaller vessels, in at least one possible
embodiment, with high length-to-diameter (L/D) ratios (cylindrical) would
be suitable. First, high L/D ratios can be achieved, more easily, for
small vessels that result in providing turbulence and good mass transport
during extraction and desorption in this cyclic process. Under these
conditions of both high extraction and desorption rates, the potential is
high to realize high oil removal rates of 90+%, up to 98+%. Second, for
smaller vessels, the volume of the vessels (V=D2L/4) can be chosen
as a function of vessel length and diameter. Once general vessel volume
and shape are chosen, a minimum residence time in the vessels should be
maintained at the treat rates sufficient to obtain high bulk removal
efficiencies.

[0061] In this type of high-pressure gas processing, it is possible to
choose a "batch-type" system or choose a "continuous-type" system. The
batch systems can be used in parallel or in series, operated on a cyclic
basis (at prescribed residence times), be sequentially loaded, processed,
and unloaded, and yield a sufficient bulk removal efficiency. The
"continuous-type" systems generally refer to a number of batch vessels,
operated sequentially, with the supercritical carbon dioxide gas flow and
the sequential loading, processing, and unloading of the feed and product
solids can be envisioned as counter current flow of the solids movement
from feed to product with respect to the flow of the supercritical carbon
dioxide. The directional loading, processing, and unloading is opposite
to the flow of the supercritical carbon dioxide. This type of
"continuous", counter current operation is generally referred to as
continuous, counter current, sequencing-batch operation. Therefore, when
there are one or two batch stages, in series or parallel, the term
"batch" tends to be used, and when there are three or more stages, if
they operate in parallel flow to the supercritical carbon dioxide, the
term "batch" is also used. However, when they operate in counter current
flow of the solids to the supercritical carbon dioxide, we call them
counter current "sequencing-batch" simulating counter current flows of
solid feed and solid product to the flow direction of the supercritical
carbon dioxide. It should be understood that "continuous" can also define
a process in which the feed and solvent are fed continuously through a
fixed system and the products are continuously removed.

[0062] For the conditions of Table 1, in order to achieve high contaminant
removals of approximately 98%, fairly low residence times of
approximately 50 minutes (as noted in Run 6 in Table 1) should be used.
In at least one possible embodiment, the process can produce high oil
removal levels, as well as produce an economical result. To obtain an
economical result, a substantial amount of feed should be treated in a
minimal time with a minimal amount of supercritical carbon dioxide (treat
ratio).

[0063] It was found in this study that it was possible to operate at
pressures up to 10,000 PSI and temperatures up to 80-100° C., to
load, process, and unload vessels (requiring filling, pressurization,
warm-up, processing, and depressurization, cool-down, and unloading) in
cycle times less than 120 minutes, typically, 30 to 60 minutes; and,
within 30 to 60 minutes, there was enough time to carry out the
labor-related loading and unloading of approximately 200 pounds of
product solids. The labor related issues may or may not involve
mechanical assistance, such as robotics, if desired. Therefore, with a
solids density of approximately 100 pounds per cubic foot, at least one
possible reactor size would be approximately 2 cubic feet based on
extracted solids. Since the feed, according to at least one possible
embodiment, can be up to 50% (by weight) contaminated oil, with the added
weight of the oil-laden feed solids, the extractor volume could be 2.5
cubic feet. It should also be noted that, according to at least one
possible embodiment, the vessel is never or rarely totally full of feed,
that is, there should be free-space in the vessels above/below the solids
for equipment design and processing reasons.

[0064] In view of the above, extractor vessels may have substantial L/D's
when the total volume per vessel is approximately 2.5 ft3. For
example, an 8-inch inner diameter vessel would be approximately 7 feet
long. For this L/D, good mass transfer characteristics can be obtained
for the extraction and desorption part of the cycle with nominal bed
pressure drops and treat ratios, and when processing in the supercritical
region, temperature and pressure control are often or sometimes critical
to maintain purities.

[0065] For treat ratios of 5 to 30 gms CO2/gm feed, for example, it
can be calculated that sufficient mass transfer will exist in the 8-inch
inner diameter vessels containing beds of solids at slightly lower
volumes. That is, in at least one possible embodiment, it may be
practiced to load the vessels with feed by using "baskets", which may be
porous in construction, by lowering such baskets of feed into the vessel,
extracting, and then raising and removing such baskets of products from
the vessel. Since the baskets may contain feed up to 300 pounds, the
baskets, in at least one possible embodiment, can be of metal or steel
construction, or other material construction, sufficient to withstand the
weight load over many repetitive loading and unloading cycles. At least a
part, if not most all, of the basket should be porous to the
supercritical carbon dioxide for successful extraction and possibly
desorption of the contaminant oil from the bed of solids.

[0066] The number of processing vessels (stages) and the sequence of
operation, co-current or counter current to the flow of supercritical
carbon dioxide, should be selected for efficiency and economic reasons.
For efficiency and economic reasons, counter current operations are
usually or often more efficient and economical for large tonnage than
co-current or batch operations for the specific separation defined and
described herein. That is, the direction of filling and emptying the
vessels is counter current to the flow of supercritical carbon dioxide.
On this basis, the number of vessels (stages) sufficient for a prescribed
treat rate is directly a function of the production rate for the entire
plant. For example, if a given 8-inch by 7-foot vessel will hold
approximately 300 pounds of feed and if N is the number of vessels, then
300N pound of feed can be processed at, say, a residence time of 60
minutes. Therefore, according to at least one possible embodiment, the
production rate (based on the feed) can be calculated as follows: For
N=4, the plant can process 1200 pounds per hour, or approximately 14.4
tons per day (T/D) of feed; and for N=3, the plant can process
approximately 10.8 T/D. If the required residence time is 120 minutes, a
similar calculation would show that for 3 stages, the production rate
would be 5.4 T/D, and for 4 stages, the production rate would be 7.2 T/D
(based on feed flow).

[0067] One feature or aspect of an embodiment is believed at the time of
the filing of this patent application to possibly reside broadly in a
method of removing oil from a mixture of granular material and oil,
comprising high speed steel swarf, said method comprising the steps of:
loading said mixture of granular material and oil into an extraction
vessel; contacting said mixture with supercritical carbon dioxide at a
pressure greater than 4300 PSI and at a temperature sufficient to remove
a substantial portion of said oil from said mixture of granular material
and oil; flowing a sufficient quantity of supercritical carbon dioxide
through said mixture for a sufficient period of time to yield a reduced
oil content solids product and supercritical carbon dioxide containing
oil from said mixture of granular material and oil; separating said
solids product from the supercritical carbon dioxide containing oil from
said solids product; and removing said solids product from the extraction
vessel.

[0068] The components disclosed in the various publications, disclosed or
incorporated by reference herein, may possibly be used in possible
embodiments of the present invention, as well as equivalents thereof.

[0069] Another feature or aspect of an embodiment is believed at the time
of the filing of this patent application to possibly reside broadly in a
method of removing oil from a mixture of granular material and oil,
comprising high speed steel swarf, said method comprising the steps of:
loading said mixture of granular material and oil into an extraction
vessel; contacting said mixture with supercritical carbon dioxide at a
pressure and at a temperature sufficient to remove a substantial portion
of said oil from said mixture of granular material and oil; flowing a
sufficient quantity of supercritical carbon dioxide through said mixture
for a sufficient period of time to yield a reduced oil content solids
product and supercritical carbon dioxide containing oil from said mixture
of granular material and oil; separating said solids product from the
supercritical carbon dioxide containing oil from said solids product; and
removing said solids product from the extraction vessel.

[0070] The purpose of the statements about the technical field is
generally to enable the Patent and Trademark Office and the public to
determine quickly, from a cursory inspection, the nature of this patent
application. The description of the technical field is believed, at the
time of the filing of this patent application, to adequately describe the
technical field of this patent application. However, the description of
the technical field may not be completely applicable to the claims as
originally filed in this patent application, as amended during
prosecution of this patent application, and as ultimately allowed in any
patent issuing from this patent application. Therefore, any statements
made relating to the technical field are not intended to limit the claims
in any manner and should not be interpreted as limiting the claims in any
manner.

[0071] Yet another feature or aspect of an embodiment is believed at the
time of the filing of this patent application to possibly reside broadly
in a method of removing oil from swarf, said method comprising the steps
of: loading said swarf into an extraction vessel; contacting said swarf
with supercritical carbon dioxide at a pressure greater than 4300 PSI and
at a temperature sufficient to remove a substantial portion of said oil
from said swarf; flowing a sufficient quantity of supercritical carbon
dioxide through said swarf for a sufficient period of time to yield a
reduced oil content solids product and supercritical carbon dioxide
containing oil from said swarf; separating said solids product from the
supercritical carbon dioxide containing oil from said solids product; and
removing said solids product from the extraction vessel.

[0072] U.S. provisional patent application 60/942,883, filed on Jun. 8,
2007, having inventors Robert J. BELTZ, Eugene J. GRESKOVICH, and Rodger
MARENTIS, Attorney Docket No. NHL-KAL-03-PROV, and title "METHOD FOR DEEP
EXTRACTION OF CONTAMINANTS FROM GRINDING SWARFS AND SIMILAR MATERIALS
USING SUPERCRITICAL CARBON DIOXIDE" is hereby incorporated by reference
as if set forth in its entirety herein.

[0073] Still another feature or aspect of an embodiment is believed at the
time of the filing of this patent application to possibly reside broadly
in a method of removing oil from swarf, said method comprising the steps
of: loading said swarf into an extraction vessel; contacting said swarf
with supercritical carbon dioxide at a pressure and at a temperature
sufficient to remove a substantial portion of said oil from said swarf;
flowing a sufficient quantity of supercritical carbon dioxide through
said swarf for a sufficient period of time to yield a reduced oil content
solids product and supercritical carbon dioxide containing oil from said
swarf; separating said solids product from the supercritical carbon
dioxide containing oil from said solids product; and removing said solids
product from the extraction vessel.

[0074] The appended drawings in their entirety, including all dimensions,
proportions and/or shapes in at least one embodiment of the invention,
are accurate and are hereby included by reference into this
specification.

[0075] A further feature or aspect of an embodiment is believed at the
time of the filing of this patent application to possibly reside broadly
in a method for separating and recycling metals and contaminant fluids
from swarf comprising the steps of: a. providing a fixed bed or beds of
contaminated feed particles in which the contaminant fluid is at any
saturation level; b. contacting said contaminated bed with supercritical
carbon dioxide (SCCO2) following at treat rates of less than 30 gm
CO2/gm of contaminated solids; c. providing the supercritical carbon
dioxide at pressures greater than 4300 PSI; d. providing sufficient
contacting time and solvent to feed ratio to yield a solids product with
a contaminant level less than 3.26% by weight (greater than 85% oil
removal), such contacting time encompassing 120 minutes or less; e.
separating the extracted contaminant by lowering the pressure (Flash) of
the Supercritical carbon dioxide-contaminant extract to remove said
contaminant by-product from the extract by flashing the carbon dioxide
and leaving the contaminant liquid; f. selecting the pressure and
temperature in the Flash to minimize oil content in the recycled carbon
dioxide; g. removing the extracted solids product from the extraction
vessel at or near ambient conditions; h. refilling the extraction vessel
and repeating steps a) through g) as timely as desired.

[0076] U.S. provisional patent application 60/942,748, filed on Jun. 8,
2007, having inventors Robert J. BELTZ, Eugene J. GRESKOVICH, and Rodger
MARENTIS, Attorney Docket No. NHL-KAL-04-PROV, and title "DEEP EXTRACTION
OF GRINDING SWARFS AND SIMILAR MATERIALS USING SUPERCRITICAL CARBON
DIOXIDE" is hereby incorporated by reference as if set forth in its
entirety herein.

[0077] Another feature or aspect of an embodiment is believed at the time
of the filing of this patent application to possibly reside broadly in
the method including at least one of (A), (B), (C), (D), (E), (F), (G),
(H), (I), (J), (K), (L), (M), (N), (O), and (P), wherein (A), (B), (C),
(D), (E), (F), (G), (H), (I), (J), (K), (L), (M), (N), (O), and (P)
comprise the following: (A) said metal waste by-product is from tool
steel swarfs; (B) said granular waste by-product is high speed steel
(HSS) grinding swarf; (C) said granular waste by-product is tungsten
carbide swarf; (D) the contaminant liquid is either oil-based and/or
aqueous-based; (E) the supercritical carbon dioxide is maintained at a
pressure level of at least 5000 PSI and a temperature of at least
60° C., to achieve greater than 88% oil removal; (F) the
supercritical carbon dioxide is maintained at a pressure of at least 8700
PSI and a temperature of at least 80° C., but at a pressure less
than 9200 PSI and temperature less than 110° C., to achieve
greater than 98.4% oil removal; (G) the contaminant oil level in the
extracted swarf product is less than 1.52% by weight; (H) the contaminant
oil level in the extracted swarf product is less than 0.44% by weight;
(I) less than 3.26% by weight contaminant is desired on the solid
product; (J) less than 1.52% by weight contaminant is desired on the
solid product; (K) less than 0.44% by weight contaminant is desired on
the solid product; (L) including a cycle of pressures and temperatures
where at or near equilibrium conditions are practiced in a process for
containment fluid removal with supercritical carbon dioxide; (M) the
contaminant fluid is a hydrocarbon or mixtures of hydrocarbons; (N) the
contaminated fluid is an aqueous contaminant; and (O) the contaminant
fluid is a mixture of hydrocarbons and aqueous-based components; and (P)
the feed solids are any solid materials with similar particle-size
ranges, yielding beds with similar porosities and mass-transfer
characteristics during processing with supercritical carbon dioxide, such
as tool steels and high speed steel.

[0078] The background information is believed, at the time of the filing
of this patent application, to adequately provide background information
for this patent application. However, the background information may not
be completely applicable to the claims as originally filed in this patent
application, as amended during prosecution of this patent application,
and as ultimately allowed in any patent issuing from this patent
application. Therefore, any statements made relating to the background
information are not intended to limit the claims in any manner and should
not be interpreted as limiting the claims in any manner.

[0079] Yet another feature or aspect of an embodiment is believed at the
time of the filing of this patent application to possibly reside broadly
in a method for treating, separating and recycling metallic solids and
contaminant fluids from high speed steel (HSS) grinding swarf such that
the product metals contain less than 2.4% (by weight) contaminant fluid
comprising the steps of: a) providing a fixed bed (stage) of feed swarf
through which supercritical carbon dioxide is passed, either up flow or
down; b) maintaining a plurality of stages through which the
supercritical carbon dioxide is passed counter current to the sequential
operation of the stages; c) filling and emptying the stages of feed swarf
and product swarf in a direction reverse of the flow of supercritical
carbon dioxide; d) providing flowing supercritical carbon dioxide at
treat ratio between 10 and 30 gms CO2/gm feed; e) maintaining the
stages at pressures greater than 4300 PSI; f) maintaining the stages at
temperatures greater than 60° C.; g) removing, on a continuous
basis, and separating the contaminant fluids in the supercritical carbon
dioxide extract by one or more stages of pressure reduction; h)
recompressing and reheating the flashed and purified carbon dioxide to
the original supercritical conditions and recycling back to the stages;
i) removing the separated contaminant fluid from the process; j) removing
the solids product, concurrent with step g), on a semi-continuous basis
for each stage, replicating a counter current movement with respect to
the flowing supercritical carbon dioxide; k) removing the solids product
when the oil content is less than 2.4% by weight; I) emptying,
recharging, and processing each stage as described in step g) with a
total cycle time less than 120 minutes for the whole process; m)
maintaining N stages within the Process, predicated by the desired
production rate; n) providing up to 120 minutes of residence time in the
extractor to permit 98+% oil removal; o) providing up to 120 minutes of
residence time for feed rates of 1 to 15 tons per day.

[0080] U.S. provisional patent application 60/942,759, filed on Jun. 8,
2007, having inventors Rodger MARENTIS, Robert J. BELTZ, and Eugene J.
GRESKOVICH, Attorney Docket No. NHL-KAL-05-PROV, and title "METHOD FOR
NEARLY COMPLETE EXTRACTION OF GRINDING SWARFS AND SIMILAR MATERIALS USING
SUPERCRITICAL CARBON DIOXIDE" is hereby incorporated by reference as if
set forth in its entirety herein.

[0081] Still another feature or aspect of an embodiment is believed at the
time of the filing of this patent application to possibly reside broadly
in the method including at least one of (A), (B), (C), (D), (E), and (F),
wherein (A), (B), (C), (D), (E), and (F) comprise the following: (A) said
high speed steel (HSS) swarf is treated such that the product metals
contain a contaminant fluid content of less than 1.5% (by weight); (B)
the product metals contain a contaminant fluid content of less than 0.44%
(by weight); (C) the contaminant fluid in high speed steel (HSS) grinding
swarf is primarily an oil-based contaminant; (D) the contaminant fluid in
high speed steel (HSS) grinding swarf is primarily an aqueous-based
contaminant; (E) the contaminant fluid in high speed steel (HSS) grinding
swarf is a co-mixture of aqueous and oil-based compounds; and (F)
including conditions that result in a metallic product that contains as
little as no (0%) contaminant, comprising the steps of: a) providing
residence times in the extractor higher than 120 minutes; b) providing
flowing supercritical carbon dioxide at treat ratios higher than 30 gms
CO2/gm feed; c) maintaining as few stages as possible, down to one
stage, predicated on the production rate desired; d) optimizing steps a)
through c) such that a preferred set of conditions yields a contaminant
level as low as possible.

[0082] All, or substantially all, of the components and methods of the
various embodiments may be used with at least one embodiment or all of
the embodiments, if more than one embodiment is described herein.

[0083] A further feature or aspect of an embodiment is believed at the
time of the filing of this patent application to possibly reside broadly
in a method for separating and recycling metals and contaminant fluids
from swarf comprising the steps of: a) providing a fixed bed or beds of
contaminated feed particles in which the contaminant is at any saturation
level; b) contacting said contaminated bed with supercritical carbon
dioxide (SCCO2) flowing at treat rates of less than 30 gms
CO2/gm sample; c) providing the supercritical carbon dioxide at
temperatures greater than 60° C., and;

d) providing the supercritical carbon dioxide at pressures greater than
4300 PSI; e) providing sufficient contacting time and solvent to feed
ratio to yield a solids product with a contaminant level less than 2.4%
by weight or other desired content level; f) separating the extracted oil
by lowering the pressure of the supercritical carbon dioxide oil extract
to remove said oil by-product from the extract; g) removing the extracted
solids product from the extraction vessel at or near ambient conditions;
h) refilling the extraction vessel and repeating steps a) through f) as
timely as desired.

[0084] The purpose of the statements about the object or objects is
generally to enable the Patent and Trademark Office and the public to
determine quickly, from a cursory inspection, the nature of this patent
application. The description of the object or objects is believed, at the
time of the filing of this patent application, to adequately describe the
object or objects of this patent application. However, the description of
the object or objects may not be completely applicable to the claims as
originally filed in this patent application, as amended during
prosecution of this patent application, and as ultimately allowed in any
patent issuing from this patent application. Therefore, any statements
made relating to the object or objects are not intended to limit the
claims in any manner and should not be interpreted as limiting the claims
in any manner.

[0085] Another feature or aspect of an embodiment is believed at the time
of the filing of this patent application to possibly reside broadly in
the method, including at least one of (A), (B), (C), (D), (E), (F), (G),
(H), and (I), wherein (A), (B), (C), (D), (E), (F), (G), (H), and (I)
comprise the following: (A) said granular metal waste by-product is high
speed steel (HSS) swarf; (B) the contaminant liquid is oil-based and/or
aqueous-based; (C) the supercritical carbon dioxide is maintained at a
pressure level of at least 5000 PSI and a temperature of at least
68° C.; (D) the supercritical carbon dioxide is maintained at a
pressure of at least 8700 PSI and a temperature of at least 80°
C., but at a pressure less than 9200 PSI and temperature less than
110° C.; (E) the contaminant oil level in the extracted swarf
product is less than 1.5% by weight; (F) the contaminant oil level in the
extracted swarf product is less than 0.45% by weight; (G) less than 2.4%
by weight contaminant is desired on the solid product; (H) less than 1.5%
by weight contaminant is desired on the solid product; and (I) less than
0.45% by weight contaminant is desired on the solid product.

[0086] All of the patents, patent applications and publications recited
herein, and in the Declaration attached hereto, are hereby incorporated
by reference as if set forth in their entirety herein.

[0087] Yet another feature or aspect of an embodiment is believed at the
time of the filing of this patent application to possibly reside broadly
in a method for separating and recycling metals and contaminant fluid
from swarf comprising the steps of: a. Providing a fixed bed of
contaminated particles in which the contaminant feed particles are
placed; b. Contacting said bed of contaminated particles with
supercritical carbon dioxide; c. Providing the supercritical carbon
dioxide at temperatures greater than 60° C. and less than
150° C.; d. Providing the supercritical carbon dioxide at
pressures greater than 5000 PSI and less than 9200 PSI; e. Providing
sufficient contacting time and solvent to feed ratio to yield a solids
product with a contaminant level less than 2.4 percent by weight; f.
Separating the extracted oil by lowering the pressure of the
supercritical carbon dioxide oil extract to remove said oil by product
from the extract; g. Removing the extracted solids product from the
extraction vessel at or near ambient conditions; h. Refilling the
extraction vessel and repeating steps a through f as timely as desired.

[0088] The summary is believed, at the time of the filing of this patent
application, to adequately summarize this patent application. However,
portions or all of the information contained in the summary may not be
completely applicable to the claims as originally filed in this patent
application, as amended during prosecution of this patent application,
and as ultimately allowed in any patent issuing from this patent
application. Therefore, any statements made relating to the summary are
not intended to limit the claims in any manner and should not be
interpreted as limiting the claims in any manner.

[0089] Still another feature or aspect of an embodiment is believed at the
time of the filing of this patent application to possibly reside broadly
in the method including at least one of (A), (B), (C), (D), (E), and (F),
wherein (A), (B), (C), (D), (E), and (F) comprise the following: (A) said
swarf comprises high speed steel HSS swarf; (B) the contaminant liquid is
oil based and/or aqueous based; (C) the supercritical carbon dioxide is
maintained at a pressure level of at least 5000 PSI and a temperature of
at least 68° C.; (D) the supercritical carbon dioxide is
maintained at a pressure level of at least 5000 PSI and a temperature of
at least 68° C.; (E) the supercritical carbon dioxide is
maintained at a pressure level of at least 5000 PSI and a temperature of
at least 68° C.; and wherein the contaminant oil level in the
extracted swarf product is less than 1.5 percent by weight; and (H) the
supercritical carbon dioxide is maintained at a pressure of at least 8700
PSI and a temperature of at least 80° C.; and wherein the
contaminant oil level in the extracted swarf product is less than 0.45
percent by weight.

[0090] It will be understood that any or all examples of patents,
published patent applications, and other documents which are included in
this application and including those which are referred to in paragraphs
which state "Some examples of . . . which may possibly be used in at
least one possible embodiment of the present application . . . " may
possibly not be used or useable in any one or more or any embodiments of
the application.

[0091] The sentence immediately above relates to patents, published patent
applications and other documents either incorporated by reference or not
incorporated by reference.

[0092] A further feature or aspect of an embodiment is believed at the
time of the filing of this patent application to possibly reside broadly
in a method for treating and separating contaminant fluids, either oil
and/or aqueous, from swarf for reuse or other industrial purposes by: (A)
a method for separating and recycling metals and contaminant fluid from
swarf comprising the steps of: a. Providing a fixed bed of contaminated
particles in which the contaminant particles are placed; b. Contacting
said bed of contaminated particles with supercritical carbon dioxide; c.
Providing the supercritical carbon dioxide at temperatures greater than
60° C. and less than 150° C.; d. Providing the
supercritical carbon dioxide at pressures greater than 5000 PSI and less
than 9200 PSI; e. Providing sufficient contacting time and solvent to
feed ratio to yield a solids product with a contaminant level less than
2.4 percent by weight; f. Separating the extracted oil by lowering the
pressure of the supercritical carbon dioxide oil extract to remove said
oil by product from the extract; g. Removing the extracted solids product
from the extraction vessel at or near ambient conditions; h. Refilling
the extraction vessel and repeating steps a through f as timely as
desired, and wherein less than 2.4 percent by weight, contaminant is
desired on the solid product.

[0093] All of the references and documents, cited in any of the documents
cited herein, are hereby incorporated by reference as if set forth in
their entirety herein. All of the documents cited herein, referred to in
the immediately preceding sentence, include all of the patents, patent
applications and publications cited anywhere in the present application.

[0094] Another feature or aspect of an embodiment is believed at the time
of the filing of this patent application to possibly reside broadly in
the method, wherein the supercritical carbon dioxide is maintained at a
pressure level of at least 5000 PSI and a temperature of at least
68° C., and wherein less than 1.5 percent by weight contaminant is
desired on the solid product.

[0095] The description of the embodiment or embodiments is believed, at
the time of the filing of this patent application, to adequately describe
the embodiment or embodiments of this patent application. However,
portions of the description of the embodiment or embodiments may not be
completely applicable to the claims as originally filed in this patent
application, as amended during prosecution of this patent application,
and as ultimately allowed in any patent issuing from this patent
application. Therefore, any statements made relating to the embodiment or
embodiments are not intended to limit the claims in any manner and should
not be interpreted as limiting the claims in any manner.

[0096] Yet another feature or aspect of an embodiment is believed at the
time of the filing of this patent application to possibly reside broadly
in the method, wherein the supercritical carbon dioxide is maintained at
a pressure level of at least 5000 PSI and a temperature of at least
68° C., and wherein less than 0.45 percent by weight contaminant
is desired on the solid product.

[0097] The details in the patents, patent applications and publications
may be considered to be incorporable, at applicant's option, into the
claims during prosecution as further limitations in the claims to
patentably distinguish any amended claims from any applied prior art.

[0098] The purpose of the title of this patent application is generally to
enable the Patent and Trademark Office and the public to determine
quickly, from a cursory inspection, the nature of this patent
application. The title is believed, at the time of the filing of this
patent application, to adequately reflect the general nature of this
patent application. However, the title may not be completely applicable
to the technical field, the object or objects, the summary, the
description of the embodiment or embodiments, and the claims as
originally filed in this patent application, as amended during
prosecution of this patent application, and as ultimately allowed in any
patent issuing from this patent application. Therefore, the title is not
intended to limit the claims in any manner and should not be interpreted
as limiting the claims in any manner.

[0099] The abstract of the disclosure is submitted herewith as required by
37 C.F.R. §1.72(b). As stated in 37 C.F.R. §1.72(b):

[0100] A
brief abstract of the technical disclosure in the specification must
commence on a separate sheet, preferably following the claims, under the
heading "Abstract of the Disclosure." The purpose of the abstract is to
enable the Patent and Trademark Office and the public generally to
determine quickly from a cursory inspection the nature and gist of the
technical disclosure. The abstract shall not be used for interpreting the
scope of the claims. Therefore, any statements made relating to the
abstract are not intended to limit the claims in any manner and should
not be interpreted as limiting the claims in any manner.

[0101] The embodiments of the invention described herein above in the
context of the preferred embodiments are not to be taken as limiting the
embodiments of the invention to all of the provided details thereof,
since modifications and variations thereof may be made without departing
from the spirit and scope of the embodiments of the invention.

Patent applications by Eugene J. Greskovich, State College, PA US

Patent applications by Robert J. Beltz, Latrobe, PA US

Patent applications in class Including regeneration, purification, recovery or separation of agent used

Patent applications in all subclasses Including regeneration, purification, recovery or separation of agent used